CA2695116C - A process of preventing polymerization of cracked volatile products during pyrolysis and gasification - Google Patents
A process of preventing polymerization of cracked volatile products during pyrolysis and gasification Download PDFInfo
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- CA2695116C CA2695116C CA2695116A CA2695116A CA2695116C CA 2695116 C CA2695116 C CA 2695116C CA 2695116 A CA2695116 A CA 2695116A CA 2695116 A CA2695116 A CA 2695116A CA 2695116 C CA2695116 C CA 2695116C
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- tar
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- gasification
- carbonaceous material
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002309 gasification Methods 0.000 title abstract description 25
- 238000000197 pyrolysis Methods 0.000 title abstract description 7
- 238000006116 polymerization reaction Methods 0.000 title abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- MCNTVOFOCCAUQI-UHFFFAOYSA-M [NH4+].C([O-])([O-])=O.[Ni+] Chemical group [NH4+].C([O-])([O-])=O.[Ni+] MCNTVOFOCCAUQI-UHFFFAOYSA-M 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002029 lignocellulosic biomass Substances 0.000 claims 1
- 239000011269 tar Substances 0.000 description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000012263 liquid product Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000002028 Biomass Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229960004592 isopropanol Drugs 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 241000609240 Ambelania acida Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 244000138286 Sorghum saccharatum Species 0.000 description 4
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 4
- 239000010905 bagasse Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical compound C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0969—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Industrial Gases (AREA)
- Processing Of Solid Wastes (AREA)
- Polymerisation Methods In General (AREA)
- Polyesters Or Polycarbonates (AREA)
- Coke Industry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention is directed towards a process of preparing a catalyzed carbonaceous material and preventing polymerization of cracked volatile products during pyrolysis or gasification of carbonaceous materials.
Description
"A PROCESS OF PREVENTING POLYMERIZATION OF CRACKED
VOLATILE PRODUCTS DURING PYROLYSIS AND GASIFICATION"
Field of the Invention The present invention is in the field of gasification technology.
Background of the Invention Biomass gasification is a complex thermo chemical process that consists of a number of elementary chemical reactions, beginning with the partial oxidation of a lignocellulosic fuel with a gasifying agent, usually air, oxygen or steam.
Biomass + 02 (or H20) -~ CO + CO2 + H20 + H2 + CH4 + other gaseous hydrocarbons + Tar + Ash In a gasification process, carbonaceous material undergoes various chemical reactions at various temperature ranges, i.e. from ambient to 1000 C. The nature of reactions is given below:
At 400-600 C: The carbonaceous material decomposes into char and volatile matter.
At 600-1000: Carbon reacts with oxygen to produce carbon dioxide and heat and subsequently the CO2 thus produced reacts with C (char) to produce CO.
At 1000 C: The steam is used to regulate the temperature and the steam used reacts with carbon to produce carbon mono-oxide and hydrogen.
The tar is formed at 400-600 C, wherein the volatile matter undergoes secondary decomposition and polymerization to produce tar. Tars are problematic in integrated biomass gasification systems for a number of reasons. Tars can condense in exit pipes and on particulate filters leading to blockages and clogged filters and other complications. As mentioned previously, existing process of gasification utilizes very complex and expensive purification system to overcome the tar problem.
Several technology such as mechanism methods (scrubbers, filters, cyclone, ESP
and RSP), self-modification methods (selecting better gasifier and optimizing operation
VOLATILE PRODUCTS DURING PYROLYSIS AND GASIFICATION"
Field of the Invention The present invention is in the field of gasification technology.
Background of the Invention Biomass gasification is a complex thermo chemical process that consists of a number of elementary chemical reactions, beginning with the partial oxidation of a lignocellulosic fuel with a gasifying agent, usually air, oxygen or steam.
Biomass + 02 (or H20) -~ CO + CO2 + H20 + H2 + CH4 + other gaseous hydrocarbons + Tar + Ash In a gasification process, carbonaceous material undergoes various chemical reactions at various temperature ranges, i.e. from ambient to 1000 C. The nature of reactions is given below:
At 400-600 C: The carbonaceous material decomposes into char and volatile matter.
At 600-1000: Carbon reacts with oxygen to produce carbon dioxide and heat and subsequently the CO2 thus produced reacts with C (char) to produce CO.
At 1000 C: The steam is used to regulate the temperature and the steam used reacts with carbon to produce carbon mono-oxide and hydrogen.
The tar is formed at 400-600 C, wherein the volatile matter undergoes secondary decomposition and polymerization to produce tar. Tars are problematic in integrated biomass gasification systems for a number of reasons. Tars can condense in exit pipes and on particulate filters leading to blockages and clogged filters and other complications. As mentioned previously, existing process of gasification utilizes very complex and expensive purification system to overcome the tar problem.
Several technology such as mechanism methods (scrubbers, filters, cyclone, ESP
and RSP), self-modification methods (selecting better gasifier and optimizing operation
2 parameters) and newly developed plasma technology have been tested with certain degree of success.
Mechanism methods only remove or capture the tar from product gases, while the energy in tar is lost. The self-modification can reduce the tar and convert the tar into useful gases; however, modification of operation parameter is at the expense of reduction in the heat value of gases. A new two-stage gasifier can produce the syngas with low tar content and high heat value.
Thermal cracking and catalytic cracking are used to decompose or reduce tar though there are still some disadvantages. In order to gets highly efficient tar decomposition, the temperature of thermal cracking needs to be very high, which can result in higher operating cost. Catalyst cracking can modify the composition of product gases at very low temperature.
For catalyst cracking shortcomings exists such as the commercial Ni-based and alkali metal catalysts will be inactive by deposited carbon and H2S, as for dolomite catalyst, broken particles also decreases the activity. Plasma technology cannot only effectively remove fly ash, NOx and SOZ, but also sharply decreases the formation of tar during biomass gasification. A novel catalytic deposition (intimate contact between biomass and the catalyst) inside the biomass can overcome the disadvantages.
US patent 20070000177A1 describes the process of low temperature catalytic gasification of carbonaceous material achieves high carbon conversion to methane at mild temperature for fuel application.
US patent 7132183 describes gasification process of carbonaceous feed stock in a gasifier with high temperature operating in the range of 700 -1600 C and a portion of gases produced there from electrochemically oxidized in a fuel cell.
W020070044342 patent describes the function of catalytic function of reforming a tar contained in the gas produced by the gasification reaction which absorbs COa
Mechanism methods only remove or capture the tar from product gases, while the energy in tar is lost. The self-modification can reduce the tar and convert the tar into useful gases; however, modification of operation parameter is at the expense of reduction in the heat value of gases. A new two-stage gasifier can produce the syngas with low tar content and high heat value.
Thermal cracking and catalytic cracking are used to decompose or reduce tar though there are still some disadvantages. In order to gets highly efficient tar decomposition, the temperature of thermal cracking needs to be very high, which can result in higher operating cost. Catalyst cracking can modify the composition of product gases at very low temperature.
For catalyst cracking shortcomings exists such as the commercial Ni-based and alkali metal catalysts will be inactive by deposited carbon and H2S, as for dolomite catalyst, broken particles also decreases the activity. Plasma technology cannot only effectively remove fly ash, NOx and SOZ, but also sharply decreases the formation of tar during biomass gasification. A novel catalytic deposition (intimate contact between biomass and the catalyst) inside the biomass can overcome the disadvantages.
US patent 20070000177A1 describes the process of low temperature catalytic gasification of carbonaceous material achieves high carbon conversion to methane at mild temperature for fuel application.
US patent 7132183 describes gasification process of carbonaceous feed stock in a gasifier with high temperature operating in the range of 700 -1600 C and a portion of gases produced there from electrochemically oxidized in a fuel cell.
W020070044342 patent describes the function of catalytic function of reforming a tar contained in the gas produced by the gasification reaction which absorbs COa
3 PCT/IB2008/001980 contained in a gas by a chemical to acceleration due to thermal transfer of flowable heat carrier and a chemical.
W02006031011 provides a gasification technique includes first stage fluidized bed catalytic gasification and second stage gasification of tar and catalytic reforming to convert nitrogen in tar and HCN in a flammable gas into NH3. The temperature of a total process is lower than the melting point of ash; powdery ash is generated and thus easily treated.
There have been extensive researches for evolving a tar free gasification process for conversion of coal or biomass into synthesis gas. The crux of tar generation process lies in reaction mechanisms involved leading to tar formation.
Till date all technologies involve tar elimination by removing the tar outside the gasifier after the gas is produced. However, no technology is available to prevent tar formation at pyrolysis step during gasification.
Object of the invention:
The object of the invention is to prevent polymerization of cracked volatile products during pyrolysis and gasification process, thereby preventing tar formation during said process.
Detailed description of the present invention:
Accordingly, the present invention is directed towards a process preparing a carbonaceous material which can be used as staring material for either pyrolysis and/
or gasification, by which tar formation can be eliminated.
In one aspect of the present invention, the invention discloses a process of preparing a catalyzed carbonaceous material, said process comprising the steps:
(a) soaking a carbonaceous material in a soluble metal salt solution, (b) drying the carbonaceous material of step (a), (c) raising the temperature of the carbonaceous material to a temperature sufficient to decompose the metal salt to its oxide and/or carbonates to obtain a catalyzed carbonaceous material.
W02006031011 provides a gasification technique includes first stage fluidized bed catalytic gasification and second stage gasification of tar and catalytic reforming to convert nitrogen in tar and HCN in a flammable gas into NH3. The temperature of a total process is lower than the melting point of ash; powdery ash is generated and thus easily treated.
There have been extensive researches for evolving a tar free gasification process for conversion of coal or biomass into synthesis gas. The crux of tar generation process lies in reaction mechanisms involved leading to tar formation.
Till date all technologies involve tar elimination by removing the tar outside the gasifier after the gas is produced. However, no technology is available to prevent tar formation at pyrolysis step during gasification.
Object of the invention:
The object of the invention is to prevent polymerization of cracked volatile products during pyrolysis and gasification process, thereby preventing tar formation during said process.
Detailed description of the present invention:
Accordingly, the present invention is directed towards a process preparing a carbonaceous material which can be used as staring material for either pyrolysis and/
or gasification, by which tar formation can be eliminated.
In one aspect of the present invention, the invention discloses a process of preparing a catalyzed carbonaceous material, said process comprising the steps:
(a) soaking a carbonaceous material in a soluble metal salt solution, (b) drying the carbonaceous material of step (a), (c) raising the temperature of the carbonaceous material to a temperature sufficient to decompose the metal salt to its oxide and/or carbonates to obtain a catalyzed carbonaceous material.
4 wherein the soluble salt is capable of decomposing into oxide and/or carbonates at a temperature which is below the decomposing temperature of the carbonaceous materials.
In another aspect the carbonaceous material is lignocelulosic biomass.
Yet in another aspect the metal salt is selected from a group comprising nickel, cobalt, iron and zinc.
In the present process the soluble salt used is nickel ammonium carbonate.
One more aspect of the present process the concentration of metal salt is in the range of 0.05% to 2%.
The decomposition temperature of the soluble salt is in the range of 150 C to 300 C.
In another embodiment of the present invention, the invention discloses a process of preventing polymerization of cracked volatile products during pyrolysis or gasification of carbonaceous materials, said process comprising pyrolyzing and/ or gasifying catalyzed carbonaceous material as obtained by the process as disclosed in the first embodiment of the invention.
In the present invention, the packed bed reactor is used in updraft mode, in which the reactive gases and nitrogen is passed at the bottom and the product gases released at the top. The pyrolytic gasification process of the catalyzed biomass is conducted with normal reforming reactants oxygen, carbon dioxide and steam, singly or in combination along with nitrogen.
Examples Example 1 Pyrolytic gasification of raw biomass at various temperatures.
The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with 10 g of raw sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations. After completion of the reaction the reactor was cooled down and char was quantified. The results are given in table 1.
In another aspect the carbonaceous material is lignocelulosic biomass.
Yet in another aspect the metal salt is selected from a group comprising nickel, cobalt, iron and zinc.
In the present process the soluble salt used is nickel ammonium carbonate.
One more aspect of the present process the concentration of metal salt is in the range of 0.05% to 2%.
The decomposition temperature of the soluble salt is in the range of 150 C to 300 C.
In another embodiment of the present invention, the invention discloses a process of preventing polymerization of cracked volatile products during pyrolysis or gasification of carbonaceous materials, said process comprising pyrolyzing and/ or gasifying catalyzed carbonaceous material as obtained by the process as disclosed in the first embodiment of the invention.
In the present invention, the packed bed reactor is used in updraft mode, in which the reactive gases and nitrogen is passed at the bottom and the product gases released at the top. The pyrolytic gasification process of the catalyzed biomass is conducted with normal reforming reactants oxygen, carbon dioxide and steam, singly or in combination along with nitrogen.
Examples Example 1 Pyrolytic gasification of raw biomass at various temperatures.
The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with 10 g of raw sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations. After completion of the reaction the reactor was cooled down and char was quantified. The results are given in table 1.
5 Table 1 gives the result of tar, char and liquid product formation at different temperatures Table 1 Temperature C Reactants Char % Liquid products Tar %
%
450 35.96 18.98 14.34 500 CO2 + 02 + 32.24 13.76 13.24 550 steam along 30.42 12.08 12.88 600 with N2 28.02 11.616 12.484 650 23.84 8.78 10.882 Example 2 Effect of 0.1 % nickel catalyst on tar removal The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with 10 g of catalyzed sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations by the following procedures. After completion of the reaction the reactor was cooled down and char was quantified.
The liquid collected in iso-propanol was steam distilled to remove both iso-propanol and other volatile organic compounds. Tar was assumed to be non-volatile and remained in the residual water. The tar was extracted using benzene and was quantified after vaporizing the benzene and weighing the residual matter as tar.
The results are given in table 2.
%
450 35.96 18.98 14.34 500 CO2 + 02 + 32.24 13.76 13.24 550 steam along 30.42 12.08 12.88 600 with N2 28.02 11.616 12.484 650 23.84 8.78 10.882 Example 2 Effect of 0.1 % nickel catalyst on tar removal The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with 10 g of catalyzed sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations by the following procedures. After completion of the reaction the reactor was cooled down and char was quantified.
The liquid collected in iso-propanol was steam distilled to remove both iso-propanol and other volatile organic compounds. Tar was assumed to be non-volatile and remained in the residual water. The tar was extracted using benzene and was quantified after vaporizing the benzene and weighing the residual matter as tar.
The results are given in table 2.
6 Table 2 gives the= result of tar, char and liquid product formation at different temperatures Table 2 Temperature C Reactants Char % Liquid products % Tar %
450 COz + 02 + steam 29 3.11 2.2 500 along with N2 25 2.89 2.12 550 24 2.58 1.7 600 21 2.43 1.2 650 19 2.1 0.7 Example 3 Effect of 0.25% nickel catalyst on tar removal The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with,10 g of catalyzed sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen- was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations. After completion of the reaction the reactor was cooled down and char was quantified. The results are given in Table 3.
Table 3 gives the result of tar, char and liquid product formation at different temperatures Table 3 Temperature C Reactants Char % Liquid products % Tar %
450 22.21 4.63 1.88 500 C02 + 02 + 22.18 5.18 1.8 550 steam along 21.54 5.4 1.54 600 with N2 18.85 3.88 0.508 650 17.78 3.19 0.502 Example 4 Effect of 0.5% nickel catalyst on tar removal
450 COz + 02 + steam 29 3.11 2.2 500 along with N2 25 2.89 2.12 550 24 2.58 1.7 600 21 2.43 1.2 650 19 2.1 0.7 Example 3 Effect of 0.25% nickel catalyst on tar removal The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with,10 g of catalyzed sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen- was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations. After completion of the reaction the reactor was cooled down and char was quantified. The results are given in Table 3.
Table 3 gives the result of tar, char and liquid product formation at different temperatures Table 3 Temperature C Reactants Char % Liquid products % Tar %
450 22.21 4.63 1.88 500 C02 + 02 + 22.18 5.18 1.8 550 steam along 21.54 5.4 1.54 600 with N2 18.85 3.88 0.508 650 17.78 3.19 0.502 Example 4 Effect of 0.5% nickel catalyst on tar removal
7 The packed bed empty reactor was preheated 40-50 C above the reacting temperature. Once the temperature is attained, the reactor was then loaded with 10 g of catalyzed sweet sorghum bagasse pellets. The reaction was carried out at a temperature of 450, 500, 550, 600 and 650 C (reacting temperature). The reactions were carried out in presence of combination of different gases wherein the flow rates of carbon dioxide at 10 L/hr, oxygen at 20% of carbon dioxide flow rate, steam at 100 ml/hr and nitrogen was kept at 10 L/hr. The decomposed liquid products in vapor form from the reactor were collected in the iso-propanol medium which was used for tar and liquid products estimations. After completion of the reaction the reactor was cooled down and char was quantified. The results are given in Table 4.
Table 4 gives the result of tar, char and liquid product formation at different temperatures Table 4 Temperature C Reactants Char % Liquid products Tar %
%
450 29.56 3.025 2.1 500 C02+02+ 30.32 3.18 0.63 550 steam along 25.65 2.9 0.54 600 with N2 23.23 2.53 0.53 650 21.02 2.06 0.50 Example 5 Analysis of liquid products from the pyrolytic gasification at 650 C
The organic liquid layer of the steam distilled liquid was analyzed using GC-MS.
The analysis showed that the liquid contains the components such as aliphatic alcohols, aldehydes, acids, phenol, phenol and benzene derivatives, toluene, furfurals and aldose. This indicates that the liquid contain no tar.
1. Operating parameters for GC-MS:
Model . 5975, Aglient make Carrier gas . Helium Flow rate . 0.8m1/min Injector temp . 220 c Column . HP-5 MS 5 % phenyl methyl siloxane (capillary) Oven temp . Ramp: 40 C for 5 min, 8 C/min; final temp 250 C hold for 5 min Electron gun . Tungsten filament.
Ion source . Electron impact ionization
Table 4 gives the result of tar, char and liquid product formation at different temperatures Table 4 Temperature C Reactants Char % Liquid products Tar %
%
450 29.56 3.025 2.1 500 C02+02+ 30.32 3.18 0.63 550 steam along 25.65 2.9 0.54 600 with N2 23.23 2.53 0.53 650 21.02 2.06 0.50 Example 5 Analysis of liquid products from the pyrolytic gasification at 650 C
The organic liquid layer of the steam distilled liquid was analyzed using GC-MS.
The analysis showed that the liquid contains the components such as aliphatic alcohols, aldehydes, acids, phenol, phenol and benzene derivatives, toluene, furfurals and aldose. This indicates that the liquid contain no tar.
1. Operating parameters for GC-MS:
Model . 5975, Aglient make Carrier gas . Helium Flow rate . 0.8m1/min Injector temp . 220 c Column . HP-5 MS 5 % phenyl methyl siloxane (capillary) Oven temp . Ramp: 40 C for 5 min, 8 C/min; final temp 250 C hold for 5 min Electron gun . Tungsten filament.
Ion source . Electron impact ionization
8 Mass analyzer . Quadrupole mass analyzer MS quadrapole temp: 150 c Detector . Electron multiplier tube.
Example 6 Analysis of gas composition from the pyrolytic gasification at 650 C
The gas from the reactor was analyzed in a Nucon gas analyzer. Measurements on volumetric concentration of H2, COZ, CH4, and CO can be done.
Table 5 gives the result of gas composition at 650 C pyrolytic gasification.
Gas composition %
CO 22.9 CO2 21.4 CH4 6.5
Example 6 Analysis of gas composition from the pyrolytic gasification at 650 C
The gas from the reactor was analyzed in a Nucon gas analyzer. Measurements on volumetric concentration of H2, COZ, CH4, and CO can be done.
Table 5 gives the result of gas composition at 650 C pyrolytic gasification.
Gas composition %
CO 22.9 CO2 21.4 CH4 6.5
Claims (5)
1. A process of preparing a catalyzed carbonaceous material, said process comprising the steps:
(a) soaking a carbonaceous material in a soluble metal salt solution, (b) drying the carbonaceous material of step (a), (c) raising the temperature of the carbonaceous material to a temperature sufficient to decompose the metal salt to at least one of its oxide and carbonates to obtain a catalyzed carbonaceous material, wherein the soluble salt is capable of decomposing into at least one of oxide and carbonates at a temperature which is below the decomposing temperature of the carbonaceous materials, and wherein the carbonaceous material is a lignocellulosic biomass.
(a) soaking a carbonaceous material in a soluble metal salt solution, (b) drying the carbonaceous material of step (a), (c) raising the temperature of the carbonaceous material to a temperature sufficient to decompose the metal salt to at least one of its oxide and carbonates to obtain a catalyzed carbonaceous material, wherein the soluble salt is capable of decomposing into at least one of oxide and carbonates at a temperature which is below the decomposing temperature of the carbonaceous materials, and wherein the carbonaceous material is a lignocellulosic biomass.
2. A process as claimed in claim 1, wherein the metal salt is selected from the group consisting of nickel, cobalt, iron and zinc.
3. A process as claimed in claim 1, wherein the soluble salt is nickel ammonium carbonate.
4. A process as claimed in claim 1, wherein the concentration of metal salt is in the range of 0.05% to 2% by weight, based on the total weight of the soluton.
5. A process as claimed in claim 1, wherein the decomposition temperature of the soluble salt is in the range of 150° C. to 300° C.
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US8592190B2 (en) * | 2009-06-11 | 2013-11-26 | Ineos Bio Limited | Methods for sequestering carbon dioxide into alcohols via gasification fermentation |
CA2832887A1 (en) | 2011-04-11 | 2012-10-18 | ADA-ES, Inc. | Fluidized bed method and system for gas component capture |
CN104812467B (en) | 2012-09-20 | 2017-05-17 | Ada-Es股份有限公司 | Method and system to reclaim functional sites on sorbent contaminated by heat stable salts |
JP6789565B2 (en) * | 2016-04-28 | 2020-11-25 | 国立大学法人東北大学 | Hydrogen gas production method and hydrogen gas production equipment |
CN108117878B (en) * | 2016-11-28 | 2020-08-11 | 中国石油化工股份有限公司 | Method and system for preparing synthesis gas by biomass microwave pyrolysis |
CN107488477A (en) * | 2017-09-01 | 2017-12-19 | 唐山市华亿生物质燃料有限公司 | Environmentally friendly biomass fuel and its production technology |
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US2799708A (en) * | 1957-07-16 | Production of higher ketones from | ||
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JPS5130172A (en) * | 1974-09-04 | 1976-03-15 | Hitachi Shipbuilding Eng Co | Haikibutsunoshorihoho |
NL7502968A (en) * | 1975-03-13 | 1976-09-15 | Stamicarbon | PROCEDURE FOR PREPARING PRECIOUS METAL CATALYSTS. |
JPS5229805A (en) * | 1975-09-02 | 1977-03-07 | Hitachi Plant Eng & Constr Co Ltd | Method for the thermal decomposition of solid waste with metal salts o r metal hydroxides |
JPS53106623A (en) * | 1977-03-01 | 1978-09-16 | Univ Tohoku | Method of recovering nickel from coal ash residue containing nickel |
US4219338A (en) * | 1978-05-17 | 1980-08-26 | Exxon Research & Engineering Co. | Hydrothermal alkali metal recovery process |
US4334893A (en) * | 1979-06-25 | 1982-06-15 | Exxon Research & Engineering Co. | Recovery of alkali metal catalyst constituents with sulfurous acid |
JPS5822508B2 (en) * | 1979-11-07 | 1983-05-09 | 東北大学長 | Coal catalytic gasification method |
CA1163595A (en) * | 1980-12-18 | 1984-03-13 | Christian Roy | Organic products and liquid fuels from lignocellulosic materials by vacuum pyrolysis |
US4592762A (en) * | 1981-10-22 | 1986-06-03 | Institute Of Gas Technology | Process for gasification of cellulosic biomass |
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US4699632A (en) * | 1983-08-02 | 1987-10-13 | Institute Of Gas Technology | Process for gasification of cellulosic materials |
EP0134344A1 (en) * | 1983-08-24 | 1985-03-20 | Exxon Research And Engineering Company | The fluidized bed gasification of extracted coal |
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